CN100481561C - Solvent processing method for raising polymer thin film solar battery effect - Google Patents

Solvent processing method for raising polymer thin film solar battery effect Download PDF

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CN100481561C
CN100481561C CN 200610173391 CN200610173391A CN100481561C CN 100481561 C CN100481561 C CN 100481561C CN 200610173391 CN200610173391 CN 200610173391 CN 200610173391 A CN200610173391 A CN 200610173391A CN 100481561 C CN100481561 C CN 100481561C
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p3ht
solvent
active layer
film
pcbm
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CN101022153A (en
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谢志元
赵云
王利祥
程延祥
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

This invention relates to a method for increasing energy conversion efficiency of polymer film solar cells, which applies a transparent ITO as the anode and Al as the cathode, in which, the anode is decorated by PEDOT:PSS and the active layer, the mixture of P3HT:PCBM, is put into a container filled with chlorobenzene or dichlorophene after it is coated to a film, solvent molecules infiltrate into the active layer to induce the P3HT to self-install to increase the sequence of the P3HT so as to increase the migration rate of film absorption and cavities, after the Al is steamed, it is annealed at high temperature to increase the performance of the device obviously.

Description

A kind of solvent processing method that improves polymer thin-film solar cell efficient
Technical field
The present invention relates to a kind of solvent processing method that improves polymer thin-film solar cell efficient.
Background technology
The thin-film solar cells of organic/conjugated polymer have inorganic solar cell incomparable advantage, as: can prepare on the substrate of softness; Can realize industrialized production in the printing process continuously; Large tracts of land covers; Be implemented in the integration on the different substrates easily; Descend significantly compared with traditional method production cost; Important ecology and advantage economically.The research and development of organic solar batteries has been subjected to people and has more and more paid attention to.
1992, it is found that conjugated polymer and fullerene (C 60) between exist ultrafast electron transfer, can realize effective separation of charge.Nineteen ninety-five, human conjugated polymer and C such as Alan J.Heeger 60Derivative PCBM blend form the network configuration of an IPN.Like this, give body and C at conjugated polymer 60Form the heterojunction structure of the high surface area of an IPN between the acceptor material, be referred to as bulk heterojunction.Bulk heterojunction structure and common planar heterojunction structure specific energy mutually more effectively improve the separative efficiency of exciton.
Stereoregulated poly-3-hexyl thiophene (P3HT) has high charge mobility and narrower energy gap, has good self assembly characteristic simultaneously, is a kind of good organic solar batteries electron donor material.To with P3HT being electron donor and with fullerene C 60Derivative [6,6]-2-phenyl C 61The active layer that-2-butyric acid formicester (PCBM) is formed for electron acceptor, ratio by change giving body and acceptor material, the means such as adding the solvent that uses man-hour and thermal annealing that change, improved the film morphology structure in the nanometer range, form being separated of nanoscale, thereby form effective charge transfer path.2005, people such as AlanJ.Heeger reported and carried out thermal anneal process P3HT:PCBM bulk heterojunction solar cell again after having steamed electrode, at 80mW/cm 2Under the simulated solar photoirradiation, energy conversion efficiency has reached 5%.People such as YangYang report improves the light absorptive and the hole mobility of film by the solvent evaporates speed of control P3HT:PCBM film, has finally improved energy conversion efficiency.
Summary of the invention
The purpose of this invention is to provide a kind of solvent processing method that improves polymer thin-film solar cell efficient.
The polymer thin-film solar cell device architecture that the present invention adopts as shown in Figure 1.Wherein: the 1st, aluminium electrode, the 2nd, the active layer that the P3HT:PCBM mixture is formed, the 3rd, PEDOT:PSS layer, the 4th, ITO electrode, the 5th, glass or flexible substrate.
The method that adopts a kind of organic solvent steam to handle active layer improves the energy conversion efficiency of polymeric acceptor heterojunction solar battery.Wherein, be before evaporation aluminium electrode, sample to be put into the container (as shown in Figure 2) that chlorobenzene or o-dichlorohenzene solvent are housed, allow the solvent vapour molecule induce the P3HT self assembly to form orderly structure.Sample after will handling is then put into vacuum system preparation aluminium electrode.Device carries out the high-temperature thermal annealing processing after having steamed electrode under inert atmosphere.
The preparation process and the condition of polymer thin-film solar cell of the present invention are: the fine strip shape indium tin oxide electro-conductive glass that etching is good cleans up and dries.Clean ito glass is placed on the carriage of spin coater, evenly be coated with completely whole slice, thin piece with filtering good polythiofuran derivative polystyrene doped sulfonic acid solutions, the control rotating speed and the time chien shih polythiofuran derivative polystyrene doped sulfonic acid form the thick film of one deck 30nm on the indium tin oxide surface, put into 120 ℃ baking oven heat 30 minutes standby;
Respectively poly-3-hexyl thiophene of electron donor and electron acceptor C 60Derivative [6,6]-2-phenyl C 61-2-methyl butyrate is made into mass percent concentration with refining organic solvent chlorobenzene in nitrogen glove box be 2% and 1.6% solution, and both by identical volume mixture together, stirring obtains mixed solution again;
The ito glass that scribbles polythiofuran derivative polystyrene doped sulfonate film is transferred in the glove box, be placed on the carriage of spin coater, to stir obtains evenly being coated with completely whole polythiofuran derivative polystyrene doped sulfonate film surface after mixed solution filters through filter again, the control rotating speed and the time chien shih mixture form poly-3-hexyl thiophene of the thick electron donor of one deck 150nm and electron acceptor C at the indium tin oxide conductive glass surface 60Derivative [6,6]-2-phenyl C 61-2-methyl butyrate film obtains the active layer that the P3HT:PCBM mixture is formed;
In large container, put into a support, pour solvent chlorobenzene or o-dichlorohenzene again into, make the solvent surface not flood support, the substrate of the active layer that spin coating is made up of the P3HT:PCBM mixture is put into large container then, logical nitrogen is driven air away, the good seal container transfers in the glove box room temperature and places and vapor away solvent, the active layer that the P3HT:PCBM mixture that obtains handling through solvent vapour is formed after 30 minutes;
The substrate that will scribble the active layer of the P3HT:PCBM mixture composition of handling through organic solvent steam is at last put into AM aluminum metallization electrode in the vacuum coating equipment, and the thickness of aluminium electrode is 100 nanometers.
The device that has steamed after the aluminium electrode is transferred in the glove box, and heat treatment is 1 minute under 150 degree, is cooled to encapsulation after the room temperature, obtains the active layer polymer thin-film solar cell of forming with the P3HT:PCBM mixture.
At 100mW/cm 2The xenon lamp irradiation is the performance of the polymer thin-film solar cell of test method preparation of the present invention down, comprises open circuit voltage, short circuit current, energy conversion efficiency and fill factor, curve factor.Table 1 is that Comparative Examples 1, embodiment 1 and embodiment 2 are at 100mW/cm 2The performance parameter of battery under the white light.As can be seen from Figure 3: utilize chlorobenzene (CB) and o-dichlorohenzene (DCB) steam treated P3HT:PCBM active layer can improve the efficient of polymer thin-film solar cell.Handle and just adopt the Solar cell performance of heat treated to be without solvent vapour: open circuit voltage 0.63V, short circuit current 8.88mA/cm 2, energy conversion efficiency is 3.43%, fill factor, curve factor is 0.613.Handle the back Solar cell performance through solvent vapour and obtained effective raising.The performance of device is open circuit voltage 0.7V under the situation of utilizing o-dichlorohenzene (DCB) steam treated, short circuit current 10.01mA/cm 2, energy conversion efficiency is 3.7%, fill factor, curve factor is 0.528; The performance of device is open circuit voltage 0.7V under the situation of utilizing chlorobenzene (CB) steam treated, short circuit current 9.39mA/cm 2, energy conversion efficiency is 3.5%, fill factor, curve factor is 0.532.
Characteristics of the present invention are the active layers with the good solvent steam treated polymer solar battery of a kind of P3HT and PCBM, P3HT component generation self assembly in the solvent molecule induced activity layer, improve its order, thereby improved the light absorptive and the hole mobility of battery.Further high-temperature thermal annealing makes the IPN path of P3HT:PCBM formation co-continuous, improves the energy conversion efficiency of battery.
The present invention will be further described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is the device architecture schematic diagram of polymer solar battery.Wherein: the 1st, aluminium electrode, the 2nd, P3HT:PCBM active layer, the 3rd, PEDOT:PSS layer, the 4th, ITO electrode, the 5th, glass or flexible substrate.
Fig. 2 is that the organic solvent steam method is handled the active layer schematic diagram.Wherein: the 6th, solvent vapour, the 7th, the active layer that the P3HT:PCBM mixture is formed, the 8th, solvent.The wide-mouth bottle that adopts one 500 milliliters is placed a support therein and is used for supporting sample as container.Inject chlorobenzene or dichloro-benzenes therein, make solvent not flood support.Having the substrate of the thick P3HT:PCBM active layer of 150nm to place spin coating wherein handled 30 minutes.
Fig. 3 is at 100mW/cm 2The xenon lamp irradiation is the performance parameter contrast of battery down.
Embodiment:
Comparative Examples 1:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, the fine strip shape ITO electro-conductive glass with certain width that etching is good cleans up and dries, clean ito glass is placed on the carriage of spin coater, evenly be coated with completely whole slice, thin piece with filtering good PEDOT:PSS solution, the control rotating speed and the time chien shih PEDOT:PSS form the film of layer of even 30 nanometers on the ito glass surface, the baking oven of putting into 120 ℃ again heated 30 minutes.
The P3HT that weighs up and PCBM are made into mass percent concentration respectively with refining organic solvent chlorobenzene in nitrogen glove box be 2% and 1.6% solution,, stirs both by identical volume mixture together again.The ito glass that scribbles the PEDOT:PSS film is transferred in the glove box, be placed on the carriage of spin coater, to dissolve good mixed solution again and after 0.45 micron filter filters, evenly be coated with completely whole PEDOT:PSS film surface, the control rotating speed and the time chien shih mixture form layer of even 150 nano thin-films on the ito glass surface.And then put into and begin to vacuumize the steaming metal aluminium electrode in the vacuum coating equipment.Be respectively 5 * 10 in vacuum degree 1The metal aluminium electrode of evaporation one bed thickness 100 nanometers under the Pascal, the effective area of battery is 12 square millimeters, making structure is the polymer solar battery of ITO/PEDOT:PSS (30nm)/P3HT:PCBM (150nm)/Al (100nm).Completed device behind the electrode 150 degree high-temperature thermal annealings 1 minute in glove box have been steamed.
Embodiment 1:
Earlier the ITO on the ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, the fine strip shape ITO electro-conductive glass with certain width that etching is good cleans up and dries, clean ito glass is placed on the carriage of spin coater, evenly be coated with completely whole slice, thin piece with filtering good PEDOT:PSS solution, the control rotating speed and the time chien shih PEDOT:PSS form the film of layer of even 30 nanometers on the ito glass surface, the baking oven of putting into 120 ℃ again heated 30 minutes.
The P3HT that weighs up and PCBM are made into mass percent concentration respectively with refining organic solvent chlorobenzene in nitrogen glove box be 2% and 1.6% solution,, stirs both by identical volume mixture together again.The ito glass that scribbles the PEDOT:PSS film is transferred in the glove box, be placed on the carriage of spin coater, to dissolve good mixed solution again and after 0.45 micron filter filters, evenly be coated with completely whole PEDOT:PSS film surface, the control rotating speed and the time chien shih mixture form layer of even 150 nano thin-films on the ito glass surface.Then sample is placed on the support in the wide-mouth bottle that the o-dichlorohenzene solvent is housed, makes solvent not flood sample, drive air in the bottle away with nitrogen again, the good seal container allows solvent gas effect film surface 30 minutes, transfers in the glove box room temperature and places solvent flashing.And then put into and begin to vacuumize the steaming metal aluminium electrode in the vacuum coating equipment.Be respectively 5 * 10 in vacuum degree 1The metal aluminium electrode of evaporation one bed thickness 100 nanometers under the Pascal, the effective area of battery is 12 square millimeters, making structure is the polymer solar battery of ITO/PEDOT:PSS (30nm)/P3HT:PCBM (150nm)/Al (100nm).Completed device behind the electrode 150 degree high-temperature thermal annealings 1 minute in glove box have been steamed.
Embodiment 2:
Device architecture and preparation method just behind the intact P3HT:PCBM film of spin coating, utilize the chlorobenzene solvent steam to replace the o-dichlorohenzene solvent vapour to handle with embodiment 1.

Claims (1)

1, a kind of solvent processing method that improves polymer thin-film solar cell efficient, it is characterized in that, the fine strip shape indium tin oxide electro-conductive glass that etching is good cleans up and dries, clean indium tin oxide electro-conductive glass is placed on the carriage of spin coater, evenly be coated with completely whole slice, thin piece with filtering good polythiofuran derivative polystyrene doped sulfonic acid solutions, the control rotating speed and the time chien shih polythiofuran derivative polystyrene doped sulfonic acid form the thick film of one deck 30nm on the indium tin oxide surface, put into 120 ℃ baking oven heat 30 minutes standby;
Respectively poly-3-hexyl thiophene of electron donor and electron acceptor C 60Derivative [6,6]-2-phenyl C 61-2-methyl butyrate is made into mass percent concentration with refining organic solvent chlorobenzene in nitrogen glove box be 2% and 1.6% solution, and both by identical volume mixture together, stirring obtains mixed solution again;
The ito glass that scribbles polythiofuran derivative polystyrene doped sulfonate film is transferred in the glove box, be placed on the carriage of spin coater, to stir obtains evenly being coated with completely whole polythiofuran derivative polystyrene doped sulfonate film surface after mixed solution filters through filter again, the control rotating speed and the time chien shih mixture form poly-3-hexyl thiophene of the thick electron donor of one deck 150nm and electron acceptor C at the indium tin oxide conductive glass surface 60Derivative [6,6]-2-phenyl C 61-2-methyl butyrate film obtains P3HT: the active layer that the PCBM mixture is formed;
In large container, put into a support, pour solvent chlorobenzene or o-dichlorohenzene again into, make the solvent surface not flood support, the substrate of the active layer that spin coating is made up of the P3HT:PCBM mixture is put into large container then, logical nitrogen is driven air away, the good seal container transfers in the glove box room temperature and places and vapor away solvent, the active layer that the P3HT:PCBM mixture that obtains handling through solvent vapour is formed after 30 minutes;
The substrate that will scribble the active layer of the P3HT:PCBM mixture composition of handling through organic solvent steam is at last put into AM aluminum metallization electrode in the vacuum coating equipment, and the thickness of aluminium electrode is 100 nanometers;
The device that has steamed after the aluminium electrode is transferred in the glove box, and heat treatment is 1 minute under 150 degree, is cooled to encapsulation after the room temperature, obtains the active layer polymer thin-film solar cell that the P3HT:PCBM mixture is formed.
CN 200610173391 2006-12-29 2006-12-29 Solvent processing method for raising polymer thin film solar battery effect Expired - Fee Related CN100481561C (en)

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